Source: TETRAMER TECHNOLOGIES,L.L.C. submitted to NRP
BIODEGRADABLE LUBRICANTS FROM RENEWABLE FEEDSTOCKS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1015985
Grant No.
2018-33610-28260
Cumulative Award Amt.
$100,000.00
Proposal No.
2018-00460
Multistate No.
(N/A)
Project Start Date
Aug 1, 2018
Project End Date
Mar 31, 2019
Grant Year
2018
Program Code
[8.8]- Biofuels and Biobased Products
Recipient Organization
TETRAMER TECHNOLOGIES,L.L.C.
657 S MECHANIC ST
PENDLETON,SC 29670
Performing Department
(N/A)
Non Technical Summary
Current agriculture and off-road equipment requires the use of lubricants to ensure efficient operation of integral hydraulic and gear driven systems. The lubricants, either oils or greases, aid in reducing friction, dissipating heat, prevent oxidation, and seal of water and debris from vital areas of the equipment. During operation, equipment may have slight leaks or suffer catastrophic failures during operation, posing a risk of the lubricant leaking into a sensitive environment. The purpose of this SBIR Program is to develop a biodegradable lubricant to replace non-biodegradable lubricants currently utilized in agriculture and off-road applications. Development and deployment of a biodegradable lubricant minimizes the risk of a hazardous chemical spill into a sensitive environment or watershed.The goal of this Phase I program is to generate a spectrum of lubricating fluids from biodegradable and renewable materials that can serve as stand-alone products or as components in a formulated system which can address the performance requirements in hydraulic and gear lubricants. The general approach to this research is to synthesize a series of lubricants and evaluate their base physical properties to down-select promising candidates for in-depth property analysis, based on the targeted commercial application.In Phase I, a multi-level factorial design will be generated to define the composition of the lubricants and to analyze the effects of said composition on the physical properties of the synthetic lubricant. Prior work has shown that this type of experimental design will generate predictive performance data for all compositions within the boundaries of the design matrix. Lubricants generated during this Phase I program will be analyzed for thermal properties, viscometrics, and wear properties utilizing standard test methods and practices.The commercial applications and general public benefits of this technology are numerous. The Environmental Protection Agency and the European Ecolabel for Lubricants currently have restrictions in place regarding the use of environmentally acceptable lubricants. Marine lubricants-for commercial vessels and those over 75 feet in length require the use of environmentally acceptable lubricants, so there is a market sector presently in place with few options that satisfy both cost and performance demands. Development of a successful lubricant under this Phase I SBIR would provide the market with a product that meets biodegradability/toxicity requirements while providing cost and performance benefits versus currently utilized environmentally acceptable lubricants. Beyond the current marine market, the development of a cost-effective high performance biodegradable lubricant could have dramatic effects on applications like agriculture, construction, off-road vehicles, and personal watercraft.Lubricants used in and around environmentally sensitive areas pose the risk of spills and leaks causing wide ranging environmental effects. To combat this risk, lubricants are being developed that are biodegradable, sourced from renewable materials, and provide both cost and performance benefits to their end users.
Animal Health Component
50%
Research Effort Categories
Basic
0%
Applied
50%
Developmental
50%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
50153992000100%
Goals / Objectives
The major goal of this research program is to develop a biodegradable EPG base oil platform for use in agricultural equipment, landscaping/turf equipment, and off-road vehicles, with a focus on two-cycle, hydraulic, and gear oils.Objective 1: Material Synthesis and Development of a Structure-Property MapThe purpose of Objective 1 is to develop and analyze the structure-property relationship for EPG base oil lubricants, based on the degree/level of propoxylation (PG#) of the backbone and fatty acid chain length (C#).To fulfill the primary goal, Tetramer will develop and implement a design of experiments (DOE) generating the EPG compositional space. The effects of fatty acid chain length (C#) and degree of propoxylation (PG#) on viscosity and thermal performance will be analyzed. The DOE serves as a construct to establish the structure-property relationship between the finished EPG and the nature of its base components. Previous research has shown that holding fatty acid composition (FAC) constant while increasing the degree of propoxylation (PG#) lowers the respective thermal properties (melt point, crystal onset, pour point) of the finished esters. These prior experiments were limited to a maximum of PG05. Prior research shows that as the C# increases from 8-18, the resultant triglycerides see a range of room temperature properties from liquid to hard, high melting (>70 oC) wax. Pure FA (C12-18) will be purchased from Sigma-Aldrich and higher PG from Dow Chemical. Lower PG materials (PG03 and 05) are available at Tetramer. Questions to be answered include:Do thermal properties of the finished esters continue to decrease as PG# increases?Is there a threshold limit for PG#?Do thermal properties of the finished esters scale linearly with C#, or is there non-linear correlation to C#?How do PG# and C# affect viscometric properties (pour point, KV) of a given ester?How does increasing PG# and increasing C# affect the stability of the finished ester (oxidative, hydrolytic)?Viscosity analysis will be conducted using in house kinematic viscosity testing apparatus (40 and 100 oC baths, numerous calibrated Canon-Fenske viscometers). Thermal performance will be evaluated using DSC to determine melt and crystallization profiles, and pour point analysis in accordance with ASTM D 97. The base viscosity and thermal parameters of each EPG composition will be put into the DOE and analyzed via linear regression for trends relating properties to composition.By performing this fundamental synthesis and analysis, Tetramer will define the performance boundaries of EPG base oils based on degree of propoxylation and fatty acid content. Prior work with the crystal modifiers for food applications has shown that the DOE methodology used under this objective is effective (90% CI) at generating a predictive property database based on fatty acid composition and properties of the desired ester product.Objective 2: Formulation of Down Selected Compositions and Development of EPG Specific ModifiersThe primary goal of Objective 2 will be to generate 2-3 formulated lubricants and subsequently re-test the DSC, KV, VI, and pour point of the improved materials. A sub-goal of this objective is to develop an additive package specific to the EPG base oil and formulate an optimal version of the best 2-3 (from Objective 1) EPG base oils. The formulated oils will then be validated through our third-party lab. The data will be added to the response map to look for dependencies and points of failure, enabling rapid prototyping for future formulations.Under the primary goal Tetramer will develop an EPG base oil to meet customer needs based on application. For example, a local robotics company may be interested in an ISO VG 100 hydraulic oil, while a local gear/transmission manufacturer may be interested an SAE 75W-140 gear oil. Once Tetramer has determined what the initial desired product(s) will be, the samples will be sent to Savant Laboratories (Midland, MI) for a battery of tests specific to the application area (e.g. Copper strip corrosion, Rust A/B, RPVOT, Four ball wear/EP, and Demulsibility for hydraulic fluids). Due to the cost, time, and volumes necessary for testing, Tetramer has limited the number of samples to undergo battery testing under this Phase I research program.The secondary goal of Objective 2 will be to develop modifiers for existing propoxylated FA esters. Harnessing the knowledge base generated during the NSF SBIR Phase I and II program, Tetramer will investigate the effects of blending the EPG base oil(s) with both TAG and other EPG modifiers in binary and ternary blends. The data gathered from these blending studies will be used to generate specific modifier packages for base oil and grease type EPG lubricant applications.Objective 3: Development of Supply and Production RelationshipsOne goal of Objective 3 is to determine initial supply and production channels for the EPG base oil. Tetramer has contacts at several suppliers, both for PG and FA, in addition to contacts at several manufacturers with capacities ranging from small pilot scale to full scale industrial production. The second goal of Objective 3 is to identify and build relationships with potential customers. A sub-goal of this objective is to partner with/gain reliable feedback from lubricant manufacturers and end users to find out what properties (4-6) are must haves for given applications. Cargill has offered to both provide feedback on the performance specification and has offered to sample high performing materials to their customers, as shown in the attached letter of support. Fuchs Lubricants has shown a high level of interest in working with Tetramer. Reliable input in the form of goalpost specifications will further aid in rapid formulation selection using the response map.The work of Objective 3 will be carried out in tandem with Objective 1 as parameters for down selecting potential products are needed for Objective 2. Tetramer is most interested in finding what end users and manufacturers desire from a biodegradable lubricant, especially one being used to replace currently utilized mineral feedstocks.
Project Methods
Efforts:Synthesize 19 foundational samples and analyze for thermal and viscosity properties.Assemble predictive databaseChoose compositions based on viscosity and thermal constraints of customersUtilize predictive database for formulationsBattery testing of down-selected formulationsApplication specific testing in accordance with ASTM, AOCSDevelop cost model for production of lubricants at multiple scalesEvaluation:Relate composition to function and use to validate predictive database (>90% CI)Compare predicted property values versus actual test dataCompare application specific test data to commercially available mineral lubricant alternativeCost/benefit analysis of new lubricant technology compared to current mineral lubricant systems

Progress 08/01/18 to 03/31/19

Outputs
Target Audience: General population Lubricant manufacturers w/ limited or no biodegradable offerings End users/ OEMs Polaris, Bobcat, John Deere, Echo, Stihl Marine engine manufacturers Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The technology was featured at the TechConnect World Innovation Conference in Boston (June 2019) enabling interaction with numerous corporate and governmental entities who may have need of a bio-based and biodegradable lubricant technology. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? During this Phase I program, esterified propoxylated glycerol (EPG) has been demonstrated to be a promising platform for bio-based and biodegradable industrial lubricants. EPG is known to be non-toxic and non-bioaccumulating, as the technology was originally developed and patented as a low-calorie fat replacer. During the previous 8+ years of working on the development and formulation of solid EPG for food uses, Tetramer has gained a deep fundamental understanding of the capabilities of EPG as a functional material. The goal of this Phase I SBIR research program was to demonstrate the technical feasibility of producing fluid EPG compositions that could act as industrial lubricants and semi-solid/solid EPG compositions that could act as thermally stable greases. Success for this program was to entail demonstration of lubricant base oil candidates with varied compositions, demonstration of solid and semi-solid compositions suitable as greases and waxes, and demonstration of a path to procure the raw materials and produce the finished lubricants capable of satisfying a large market volume (millions of gallons). Objective 1: Material Synthesis and Development of a Structure-Property Map [100%] Objective 2: Formulation of Down Selected Compositions and Development of EPG Specific Modifiers [100%] Objective 3: Development of Supply and Production Relationships [100%] 100 compositional variations of EPG lubricants were synthesized during this Phase I research program. The EPG compositions developed under this Phase I SBIR research program clearly demonstrate the technical potential of EPG as base oils for industrial lubricants. It is apparent that there are numerous ways to produce EPG lubricants which can meet a range of ISO VG (46-68) while maintaining pour points below 0°C. Utilization of a robust Design of Experiments (DoE) software package enabled the production of predictive response maps (thermal properties, viscometrics) and provided a tool for rapid selection and development of prototype EPG lubricant compositions. The work conducted under this objective has positioned Tetramer to be responsive and reliable in the materials it provides as candidate lubricants to customers and development partners going forward. In addition to demonstrating the initial performance based technical goals of this Phase I research program, a path to commercialization was crucial as both a raw material and production supply chain needed to be developed. Quite often new technologies are developed and fail because they cannot be produced in an economical manner based on intended application or they simply cannot be produced at the scale required by a given application. During this research program both supply, and production capabilities were validated at industrial scales (tank truck/tank car). Additionally, the cost profile of the EPG lubricants was confirmed to fall within the cost range of current synthetic esters and polyalphaolefin high-performance lubricants. While additional research and development must still be carried out to fine tune the EPG lubricants to meet application specific parameters, it is apparent that these novel materials are a platform technology suitable as lubricating base oils, process oils, and functional pastes/waxes.

Publications


    Progress 08/01/18 to 03/31/19

    Outputs
    Target Audience: General population Lubricant manufacturers with limited or no biodegradable offerings E.g. Texas Refinery Corp., Royal Purple, and Calumet End users/ equipment manufacturers E.g. Polaris, Bobcat, John Deere, Echo/Stihl Marine engine manufacturers E.g. Mercury Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

    Impacts
    What was accomplished under these goals? The purpose of this Phase I USDA-NIFA SBIR program is the commercialization of the bio-based, biodegradable materials platform, esterified propoxylated glycerol (EPG) as hydraulic fluids, gear oils, 2-cycle, and marine lubricants. The material being pursued under this research program are derived from propoxylated glycerol (PG) and varied fatty acids, generating a molecule with 53-83% of its mass coming from seed/vegetable oil sources. During the first half of this Phase I SBIR program, Tetramer has successfully created a large sample matrix that enables the mapping of structure property relationships for various EPG materials, has discovered commercial interest in both the lubricant and non-lubricant EPGs, and has learned that EPG is cost advantaged versus commercially available synthetic esters. During the second half of this Phase I program, Tetramer will bolster its existing commercial relationships and investigate additional uses (transformer fluids) for the functional EPG materials. The research tasks for this program have been split into three objectives: Objective 1: Material Synthesis and Development of a Structure-Property Map. [95%] Objective 2: Formulation of Down Selected Compositions and Development of EPG Specific Modifiers. [0%] Objective 3: Development of Supply and Production Relationships. [75%] The primary focus has been the synthesis and in-house analysis of samples (A total of 96 samples) used to develop the fundamental property map. The materials synthesized contain four different degrees of propoxylation (Glycerol, PG03, PG05, PG10) and varied combinations of the most abundant saturated fatty acids (C12, C14, C16, C18). The analyses performed at Tetramer consisted of thermal analysis via differential scanning calorimetry (DSC), pour point, fatty acid content by gas chromatography (FAC, GC), kinematic viscosity and viscosity index (KV40, KV100, VI), and titrations for acid and hydroxyl values (AV, OHV). All data generated is aggregated and used to populate the design of experiments (DOE) using the software Design Expert 11, which enables the generation of predictive property maps based on material properties and desired response factor. In addition to the fundamental research conducted under Objective 1, Tetramer has contacted both raw materials suppliers and potential production partners, to begin developing a sound commercialization profile for this material. Modification of the synthetic process allowed Tetramer to increase synthetic throughput by three times, enabling production of the entire 96 sample matrix during the first half of the research program and putting the program 2 months ahead of schedule. The samples produced range in consistency from waxes and semi-solids to low-temperature fluids. This is significant because we have found commercial interest in the potential use of EPG in non-lubricant applications. As the initial commercial target of this program is a biodegradable lubricant, Tetramer has chosen its best candidate (PG10-C12) and scaled-up to 2.5 kg production for third-party performance analysis. Both historical data and preliminary test suggest the fluid EPGs will perform quite well as lubricants in non-crankcase applications. With fluid EPG being developed for lubricants, there is an opportunity to utilize solid and semi-solid EPGs in commercial products. In an effort to scope the potential for these materials, Tetramer has signed a non-disclosure agreement with a large agriculture and industrial products company. Initial conversations have been promising with interest in semi-solid EPG as a potential petroleum jelly replacement. This relationship will be further developed during the second half of the Phase I SBIR program and into a Phase II SBIR program. Early price quotes from raw materials suppliers show a 12.5% cost reduction for EPG versus current synthetic esters. Additionally, prospective production partners have indicated similar costs for the synthetic processes for both the EPG and synthetic esters, giving EPG a cost advantaged position versus current commercially available ester lubricants.

    Publications